KR20210061997A - Photosensitive resin composition, resin sheet, cured film, organic EL display device, semiconductor electronic component, semiconductor device, and manufacturing method of organic EL display device - Google Patents

Abstract

The present invention relates to a photosensitive resin composition with high sensitivity, high bending resistance of a cured film, and high long-term reliability when a cured film is used in an organic EL display device. The present invention is a photosensitive resin composition containing an alkali-soluble resin (a), a phenol resin (b) having a halogen atom, and a photosensitive compound (c).

Description

Photosensitive resin composition, resin sheet, cured film, organic EL display device, semiconductor electronic component, semiconductor device, and manufacturing method of organic EL display device

The present invention relates to a photosensitive resin composition containing an alkali-soluble resin, a phenol resin having a halogen atom, and a photosensitive compound.

In display devices having thin displays such as smartphones, tablet PCs, and televisions, many products using organic electroluminescent (hereinafter, "organic EL") display devices have been developed.

In general, an organic EL display device has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light emitting layer, and a second electrode on a substrate, and emits light by applying a voltage between the opposing first electrode and the second electrode. I can. Among these, as a material for a planarization layer and a material for an insulating layer, a photosensitive resin composition capable of patterning by irradiation with ultraviolet rays is generally used. Among them, a photosensitive resin composition using a polyimide-based or polybenzoxazole-based resin is suitable for providing a highly reliable organic EL display device because the resin has high heat resistance and has few gas components generated from the cured film. It is used for example (see, for example, Patent Document 1).

On the other hand, in order to shorten the exposure time from reasons such as an increase in the size of the substrate or improvement in productivity, higher sensitivity is required for the photosensitive resin composition.

As a photosensitive resin composition capable of high sensitivity, it has been studied to mix a novolac resin or a polyhydroxystyrene resin with a polyimide resin or a polybenzoxazole resin (for example, see Patent Document 2). However, conventional novolac resins and polyhydroxystyrene resins have a problem in that heat resistance and mechanical properties are low.

In recent years, development of a flexible organic EL display device formed on a resin film substrate has been actively conducted. In a flexible organic EL display device, there is a bent portion and/or a portion fixed in a bent state on a structure, and a bending stress is applied to the planarization layer or the insulating layer in the bent portion. In a flexible organic EL display device including such a bent portion, high bending resistance is required for a material for a planarization layer and a material for an insulating layer. From this fact, development of a photosensitive resin composition capable of patterning with high sensitivity and obtaining a cured film having high bending resistance is strongly desired.

For these problems, for example, a method of obtaining a resin composition containing a novolac resin using bisphenol A, a polyamide resin, and an o-quinonediazide compound has been proposed (see, for example, Patent Document 3).

Japanese Patent Publication No. 2002-91343 Japanese Patent Publication No. 2008-268788 Japanese Patent Publication No. 2015-187668

However, in the photosensitive resin composition obtained by the method described in Patent Literature 3, although the sensitivity and mechanical properties of the cured film are improved, the problem that long-term reliability when the cured film is used in an organic EL display device is insufficient has been revealed. The demand for high reliability of organic EL display devices is becoming strict year by year, and materials for flattening layers and insulating layers are also required for materials that can maintain high film properties even after reliability tests under accelerated conditions such as high temperature, high humidity, and light irradiation. Has become. Therefore, it is an object of the present invention to provide a photosensitive resin composition with high sensitivity, high bending resistance of a cured film, and high long-term reliability when a cured film is used in an organic EL display device.

The present invention is a photosensitive resin composition containing an alkali-soluble resin (a), a phenol resin (b) having a halogen atom, and a photosensitive compound (c).

The photosensitive resin composition of the present invention is highly sensitive and has high bending resistance of the cured film, and a photosensitive resin composition having high long-term reliability when the cured film is used in an organic EL display device can be obtained.

1 is a cross-sectional view of an example of a TFT substrate.
2 is an enlarged cross-sectional view of an example of a pat portion of a semiconductor device having bumps.
3 is a schematic diagram showing an example of a method for manufacturing a semiconductor device having bumps.
4 is a schematic diagram of a manufacturing procedure of an organic EL display device in the embodiment.
5 is a schematic diagram of evaluation of bending resistance in Examples.

An embodiment of the present invention will be described in detail.

The photosensitive resin composition of the present invention includes an alkali-soluble resin (a), a phenol resin (b) having a halogen atom, and a photosensitive compound (c).

<Alkali-soluble resin (a)>

The photosensitive resin composition of this invention contains an alkali-soluble resin (a). Alkali solubility in the present invention means that a solution in which a resin is dissolved in γ-butyrolactone is applied on a silicon wafer, and prebaked at 120° C. for 4 minutes to form a prebaked film having a thickness of 10 μm±0.5 μm, This prebaked film is immersed in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23±1° C. for 1 minute, and then the dissolution rate determined from the decrease in the film thickness when rinsed with pure water is 50 nm/min or more.

The alkali-soluble resin (a) in the present invention has a hydroxyl group and/or an acidic group in the structural unit of the resin and/or at its main chain terminal in order to impart alkali solubility. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group. In addition, it is preferable that the alkali-soluble resin (a) has a fluorine atom in order to impart water repellency.

Examples of the alkali-soluble resin (a) in the present invention include polyimide, polyimide precursor, polybenzoxazole precursor, polyamideimide, polyamideimide precursor, polyamide, polymer of radically polymerizable monomer having an acidic group, and phenol resin. Etc. are mentioned, but it is not limited to this. You may contain 2 or more types of these resins. Among these alkali-soluble resins (a), polyimide has high development adhesion, excellent heat resistance, and a low amount of outgas under high temperature, so that long-term reliability when a cured film described later is used in an organic EL display device is high. At least one selected from the group consisting of mid, polybenzoxazole, polyamideimide, precursors of any of them, and copolymers thereof is preferable, and polyimide, polybenzoxazole, polyamideimide, precursors of any of them or their A copolymer is more preferable, and a polyimide, a polyimide precursor, a polybenzoxazole precursor, or a copolymer thereof is particularly preferable. Further, from the viewpoint of further improving the sensitivity, a polyimide precursor or a polybenzoxazole precursor is more preferable. Here, the polyimide precursor refers to a resin converted into polyimide by heat treatment or chemical treatment, and examples thereof include polyamic acid and polyamic acid ester. The polybenzoxazole precursor refers to a resin converted into polybenzoxazole by heat treatment or chemical treatment, and examples thereof include polyhydroxyamide.

The polyimide precursor and the polybenzoxazole precursor described above have a structural unit represented by the following general formula (3), and the polyimide has a structural unit represented by the following general formula (4). Two or more of these may be contained, and a resin obtained by copolymerizing the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) may be contained.

In General Formula (3), X represents a 2 to octavalent organic group, and Y represents a 2 to 11 valent organic group. R ¹¹ and R ¹³ represent a hydroxyl group or a sulfonic acid group, and each may be single or may be mixed. R ¹² and R ¹⁴ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. t, u, and w represent an integer of 0 to 3, and v represents an integer of 0 to 6. However, it is t+u+v+w>0.

In General Formula (4), E represents a 4-10 valent organic group, and G represents a 2-8 valent organic group. R ¹⁵ and R ¹⁶ represent a carboxyl group, a sulfonic acid group or a hydroxyl group. A plurality of R ¹⁵ and R ¹⁶ may be the same or different, respectively. Each of x and y independently represents an integer of 0 to 6. However, it is x+y>0.

It is preferable that a polyimide, a polyimide precursor, a polybenzoxazole precursor, or a copolymer thereof has 5 to 100,000 structural units represented by the general formula (3) or (4). Further, in addition to the structural unit represented by the general formula (3) or (4), you may have other structural units. In this case, it is preferable to have 50 mol% or more of all structural units of the structural unit represented by general formula (3) or (4).

In the general formula (3), X(R ¹¹ ) _t (COOR ¹² ) _u represents an acid residue. X is a 2 to octavalent organic group, and among them, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

Examples of the acid include dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid. Tricarboxylic acids such as acid, trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid, pyromellitic acid, 3,3',4,4'-biphenyltetracar Acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetra Carboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3- Dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl) )Methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalene Tetracarboxylic acid, 2,3,5,6-pyridine tetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, and aromatic tetracarboxylic acid or butanetetracarboxylic acid having the structure shown below And tetracarboxylic acids such as aliphatic tetracarboxylic acids such as acids and aliphatic tetracarboxylic acids containing cyclic aliphatic groups such as 1,2,3,4-cyclopentanetetracarboxylic acid. You may use 2 or more types of these.

R ²⁰ represents an oxygen atom, C(CF ₃ ) ₂ or C(CH ₃ ) ₂ . R ²¹ and R ²² each independently represent a hydrogen atom or a hydroxyl group.

Among the above acids, in the case of a tricarboxylic acid or a tetracarboxylic acid, one or two carboxyl groups ^{correspond to (COOR 12} ) in the general formula (3).

These acids may be used as they are, or may be used as an acid anhydride, an active ester, or an active amide. As an active ester, for example, an N-hydroxysuccinimide ester compound obtained by reacting a carboxyl group of an acid with N-hydroxysuccinimide. As an active amide, for example, the carboxyl group of an acid is N,N'-carbohydrate. And N-acylimidazole compounds obtained by reacting with nildiimidazole.

In the general formula (4), E(R ¹⁵ ) _x represents a residue of an acid dianhydride. E is a tetravalent to tenvalent organic group, and among them, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

Specific examples of the acid dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,3,3',4'-biphenyltetracarboxylic dianhydride. , 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzo Phenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis( 3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3- Dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxy) Phenyl)fluorenic acid dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorenic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoro Aromatic tetracarboxylic dianhydrides such as propane dianhydride and acid dianhydrides of the structures shown below, aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride, 1,2,3,4-cyclo And aliphatic tetracarboxylic dianhydrides containing cyclic aliphatic groups such as pentane tetracarboxylic dianhydride. You may use 2 or more types of these.

R ²⁰ represents an oxygen atom, C(CF ₃ ) ₂ or C(CH ₃ ) ₂ . R ²¹ and R ²² each independently represent a hydrogen atom or a hydroxyl group.

Y(R ¹³ ) _v (COOR ¹⁴ ) _w of the general formula (3) and G(R ¹⁶ ) _y of the general formula (4) represent a diamine residue. Y is a 2 to 11 valent organic group, G is a 2 to 8 valent organic group, and among them, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

Specific examples of diamine include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1 ,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy) ratio Phenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2, 2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl , 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2 '-Di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 2,2'-bis(trifluoromethyl)-5,5 '-Dihydroxy benzidine, 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, compounds in which at least a part of the hydrogen atoms of these aromatic rings are substituted with an alkyl group or a halogen atom, etc. And aliphatic diamines containing cyclic aliphatic groups such as aromatic diamine, cyclohexyldiamine, and methylenebiscyclohexylamine, and diamines having the structures shown below. You may use 2 or more types of these.

R ²⁰ represents an oxygen atom, C(CF ₃ ) ₂ or C(CH ₃ ) ₂ . R ²¹ to R ²⁴ each independently represent a hydrogen atom or a hydroxyl group.

These diamines may be used as they are, and may be used as, for example, a diisocyanate compound obtained by reacting the amino group of a diamine with phosgene, or as a trimethylsilylated diamine obtained by reacting the amino group of a diamine with chlorotrimethylsilane.

Further, by sealing the ends of these resins with a monoamine having an acidic group, an acid anhydride, an acid chloride, a monocarboxylic acid, or an active ester compound, a resin having an acidic group at the end of the main chain can be obtained.

Preferred examples of the monoamine having an acidic group include 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4,6-dihydroxy And pyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. You may use 2 or more types of these.

Preferable examples of the acid anhydride include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride. You may use 2 or more types of these.

Preferred examples of the monocarboxylic acid include 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, and 4-carboxythiophenol. You may use 2 or more types of these.

As a preferred example of the acid chloride, a monoacid chloride compound in which the carboxy group of the monocarboxylic acid is acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxinaphthalene, 1,6-di Monoacid chloride compounds in which only one carboxy group is acid chlorided among dicarboxylic acids such as carboxinaphthalene, 1,7-dicarboxinaphthalene, and 2,6-dicarboxinaphthalene. You may use 2 or more types of these.

Preferred examples of the active ester compound include a reaction product of the monoacid chloride compound and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxyimide. You may use 2 or more types of these.

The alkali-soluble resin (a) in the present invention is synthesized by a known method.

As a manufacturing method of the polyamic acid which is a polyimide precursor, a method of making a tetracarboxylic dianhydride and a diamine compound react in a solvent at low temperature is mentioned, for example.

Similarly, as a method for producing a polyamic acid ester that is a polyimide precursor, in addition to the method of reacting the polyamic acid described above with an esterifying agent, a diester is obtained with a tetracarboxylic dianhydride and an alcohol, and thereafter, the presence of a condensing agent. A method of reacting in an amine and a solvent under. A method of obtaining a diester with a tetracarboxylic dianhydride and an alcohol, and then acid chloride of the remaining dicarboxylic acid and reacting in an amine and a solvent, etc. are mentioned. From the viewpoint of ease of synthesis, it is preferable to include a step of reacting a polyamic acid with an esterifying agent. There is no restriction|limiting in particular as an esterifying agent, Although a well-known method can be applied, N,N-dimethylformamide dialkylacetal is preferable from the point that purification of the obtained resin is easy.

As a method for producing polyhydroxyamide which is a polybenzoxazole precursor, a method of condensation reaction of a bisaminophenol compound and a dicarboxylic acid in a solvent is exemplified. Specifically, for example, a method of reacting a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC) with an acid, and adding a bisaminophenol compound thereto, bisaminophenol in which a tertiary amine such as pyridine is added. A method of dropping a solution of dicarboxylic acid dichloride into the solution of the compound, etc. are mentioned.

Examples of the method for producing polyimide include a method of dehydrating and ring-closing the polyamic acid or polyamic acid ester obtained by the above-described method in a solvent. Examples of the dehydration ring closure method include chemical treatment with an acid or a base, heat treatment, and the like.

Examples of the method for producing polybenzoxazole include a method of dehydrating and ring-closing the polyhydroxyamide obtained by the above-described method in a solvent. Examples of the dehydration ring closure method include chemical treatment with an acid or a base, heat treatment, and the like.

Examples of the polyamideimide precursor include a tricarboxylic acid, a corresponding tricarboxylic anhydride, a tricarboxylic anhydride halide and a polymer of a diamine compound, and a polymer of trimellitic anhydride and an aromatic diamine compound is preferable. As a method for producing the polyamideimide precursor, a method of reacting a diamine compound such as a tricarboxylic acid, a corresponding tricarboxylic anhydride, a tricarboxylic anhydride halide or the like in a solvent at a low temperature, for example, may be mentioned.

Examples of the method for producing the polyamideimide include a method of reacting trimellitic anhydride and an aromatic diisocyanate in a solvent, and a method of dehydrating and ring-closing the polyamideimide precursor obtained by the above-described method in a solvent. Examples of the dehydration ring closure method include chemical treatment with an acid or a base, heat treatment, and the like.

The polymerization solvent is not particularly limited, and alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether, alkyl acetates such as propyl acetate, butyl acetate, and isobutyl acetate, methyl isobutyl ketone, methyl Ketones such as propyl ketone, alcohols such as butyl alcohol and isobutyl alcohol, ethyl lactate, butyl lactate, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, 3-methoxybutyl acetate, ethylene glycol monoethyl ether acetate, gamma butyrolactone, N-methyl-2-pyrrolidone, diacetone alcohol, N-cyclohexyl-2-pyrrolidone, N,N-dimethylform Amide, N,N-dimethylacetamide, dimethyl sulfoxide, propylene glycol monomethyl ether acetate, N,N-dimethylisobutyric acid amide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylpropylene urea, deltavalerolactone, 2-phenoxyethanol, 2-pyrrolidone, 2-methyl-1, 3-propanediol, diethylene glycol butyl ether, triacetin, butyl benzoate, cyclohexylbenzene, bicyclohexyl, o-nitroanisole, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, N-(2- Hydroxyethyl)-2-pyrrolidone, N,N-dimethylpropanamide, N,N-dimethylisobutylamide, N,N,N',N'-tetramethyl urea, 3-methyl-2-oxazoli Dinon, etc. are mentioned.

<Phenol resin (b) having a halogen atom>

The photosensitive resin composition of the present invention contains a phenol resin (b) having a halogen atom (hereinafter, simply referred to as "phenol resin (b)" in some cases). By containing the phenol resin (b), long-term reliability when the cured film of the present invention described later is used as a planarization layer and/or an insulating layer of an organic EL display device can be improved.

Specific examples of the halogen atom substituted form include a halogen atom, a halo(cyclo)alkyl group, or a haloaryl group, and combinations thereof. In addition, a halo(cyclo)alkyl group refers to an alkyl group, a cycloalkyl group, and a haloaryl group in which at least a part is halogenated, and the aryl group in which at least part is halogenated. As a haloalkyl group, a trihalomethyl group, a pentahaloethyl group, etc. are mentioned, for example. As a haloaryl group, a dihalophenyl group, a pentahalophenyl group, etc. are mentioned, for example. When the substituent having a halogen atom is a divalent or more group, the remaining bonding hand forms a bond with an arbitrary atom or a substituent, and may be connected to the main chain of the phenol resin (b) through another substituent. It is preferable that the halogen atom of the phenol resin (b) having a halogen atom contains a fluorine atom. By having a fluorine atom, water repellency is imparted to the surface of the film during alkali development, and soaking from the surface can be suppressed. Therefore, when a positive photosensitive resin composition is used, film reduction during development is suppressed, and a photosensitive resin film having a high residual film rate after development is obtained.

Examples of phenolic resins include novolac resins and resol resins, by polycondensing various phenols alone or a mixture thereof with aldehydes such as formalin, or polycondensing a methylol compound of phenols and phenols. Is obtained. The phenol resin having a halogen atom in the present invention is obtained by using phenols having a halogen atom.

As specific examples of phenols having a halogen atom, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,4-difluorophenol, 2,6-difluorophenol, 3,4- Difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, 2,3,5,6-tetrafluorophenol, penta Fluorophenol, 2,3,5,6-tetrafluoro-4-trifluoromethylphenol, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenol, perfluoro-1- Naphthol, perfluoro-2-naphthol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 2,6-dichlorophenol, 3,4-dichlorophenol, 3,5- Dichlorophenol, 2,4,6-trichlorophenol, 3,4,5-trichlorophenol, 2,3,5,6-tetrachlorophenol, pentachlorophenol, 2,3,5,6-tetrachloro- 4-trichloromethylphenol, 2,3,5,6-tetrachloro-4-pentachloro phenylphenol, perchloro-1-naphthol, perchloro-2-naphthol, 2-bromophenol, 3-bromophenol , 4-bromophenol, 2,4-dibromophenol, 2,6-dibromophenol, 3,4-dibromophenol, 3,5-dibromophenol, 2,4,6-t Ribromophenol, 3,4,5-tribromophenol, 2,3,5,6-tetrabromophenol, pentabromophenol, 2,3,5,6-tetrabromo-4-tribromo Methylphenol, 2,3,5,6-tetrabromo-4-pentabromophenylphenol, perbromo-1-naphthol, perbromo-2-naphthol, 2-iodophenol, 3-iodophenol, 4 -Iodophenol, 2,4-diiodophenol, 2,6-diiodophenol, 3,4-diiodophenol, 3,5-diiodophenol, 2,4,6-triiodo Phenol, 3,4,5-triiodophenol, 2,3,5,6-tetraiodophenol, pentaiodophenol, 2,3,5,6-tetraiodo-4-triiodomethylphenol , 2,3,5,6-tetraiodo-4-pentaiodophenylphenol, periodone-1-naphthol, periododo-2-naphthol, 2-(trifluoromethyl)phenol, 3-( Trifluoromethyl)phenol, 4-(trifluoromethyl)phenol, 2,6-bis(trifluoromethyl)phenol, 3,5-bis(trifluoromethyl)phenol, 2,4,6-tris (Trifluoromethyl) pe Nor, bisphenol AF, and the like, and these can be used alone or as a mixture thereof.

In addition, as aldehydes used for polycondensation with novolac resins and resol resins, in addition to formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, etc. can be mentioned, these alone or in mixtures thereof Can be used as.

The methylol compounds of phenols are those obtained by methylolating the phenols described above with formaldehyde or the like, and have at least one methylol group in the molecule.

Further, the phenol resin (b) used in the present invention may contain a structure derived from other phenols in addition to the phenols having a halogen atom within the range not deteriorating the above-described properties. In the case of containing a structure derived from other phenols, it is preferable to have 50 to 100 mol% of a structural unit derived from phenols having a halogen atom as a repeating unit with respect to 100 mol% of all repeating units of the phenol resin (b). By setting it as such a range, long-term reliability when the cured film of the present invention described later is used as a planarization layer and/or an insulating layer of an organic EL display device can be improved.

As other phenols, specifically, phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3, 4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylenebisphenol , Methylenebisp-cresol, resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-me Toxicphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropyl Phenol, α-naphthol, β-naphthol, bisphenol A, bisphenol F, bisphenol Z, bisphenol E, bisphenol C, bisphenol G, bisphenol M, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol S, 2,2'-dihydro Roxybenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4 , 4'-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, etc., and these may be used alone, Or they can be used as a mixture.

The phenol resin (b) is a general formula (1) and/or general formula (2) from the viewpoint of further improving the long-term reliability when the cured film of the present invention described later is used as a planarization layer and/or an insulating layer of an organic EL display device. It is preferred to have a structural unit represented by ). General formula (1) and/or general formula (2) represent the structural unit of a phenol resin derived from bisphenols.

In general formulas (1) and (2), A represents a divalent substituent having a halogen atom. R ¹ , R ² , R ⁵ , and R ⁶ each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, a methylol group, or an alkoxymethyl group. R ³ , R ⁴ , R ⁷ , and R ⁸ each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 10 carbon atoms. p is 0 to 2, q is 0 to 4, r and s are integers of 0 to 3.

As A, for example -CF ₂ -, -CCl ₂ -, -CBr ₂ -, -CI ₂ -, -C(CF ₃ ) ₂ -, -C(CCl ₃ ) ₂ -, -C(CBr ₃ ) Divalent substituents, such as ₂ -and -C(CI ₃ ) _{2 -, are mentioned. It is preferable to contain a fluorine atom, and -C(CF 3} ) ₂ -is more preferable from the viewpoint of industrial availability and the improvement of the film residual rate after development due to the water repellency of fluorine.

As a phenol resin having a structural unit represented by general formula (1) and/or general formula (2), for example, there are novolac resins and resol resins, and various bisphenols alone or a mixture thereof may be used as formalin. It is obtained by polycondensation with aldehydes. The resin having the structural unit represented by the general formula (1) and/or the general formula (2) is obtained by using bisphenols having a halogen atom.

As specific examples of bisphenols having a halogen atom, bisphenol AF, 2,2-bis(4-hydroxyphenyl)hexachloropropane, 2,2-bis(4-hydroxyphenyl)hexabromopropane, 2,2 -Bis(4-hydroxyphenyl)hexaiodopropane, and these may be used alone or as a mixture thereof.

In addition, as aldehydes used for polycondensation with novolac resins and resol resins, in addition to formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxy benzaldehyde, chloroacetaldehyde, etc. can be mentioned, these alone or in mixtures thereof Can be used as.

The phenol resin (b) used in the present invention may have a structure other than the structural unit represented by the general formula (1) and/or the general formula (2), but constituting the phenol resin (b) having a halogen atom It is preferable to have 50 mol% or more as a repeating unit of the structural unit represented by general formula (1) and/or general formula (2) with respect to 100 mol% of all repeating units. By setting it as such a range, long-term reliability when the cured film of this invention mentioned later is made into the planarization layer and/or the insulating layer of an organic electroluminescent display device can be improved more. It is more preferably 80 mol% or more, and particularly preferably 100 mol%.

The phenol resin (b) refers to a polystyrene-equivalent weight average molecular weight (Mw) of 500 or more. 50000 or less are preferable and, as for Mw, 10000 or less are more preferable. By making the weight average molecular weight in terms of polystyrene 500 or more, the solubility in an alkali developer can be easily adjusted to a desired range. On the other hand, by setting the weight average molecular weight in terms of polystyrene to 50000 or less, the coatability and developability of the photosensitive resin composition can be improved.

In the present invention, the content of the phenol resin (b) is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more with respect to 100 parts by mass of the alkali-soluble resin (a) from the viewpoint of improving long-term reliability. On the other hand, from the viewpoint of improving the bending resistance, 100 parts by mass or less are preferable, and 50 parts by mass or less are more preferable.

<Photosensitive compound (c)>

The photosensitive resin composition of this invention contains a photosensitive compound (c). As the photosensitive compound (c), a photoacid generator (c1), a photoinitiator (c2), etc. are mentioned. The photoacid generator (c1) is a compound that generates an acid by irradiation with light, and the photopolymerization initiator (c2) is a compound that generates radicals by cleaving and/or reacting bonds by exposure.

The content of the photosensitive compound (c) is preferably 25 to 100 parts by mass with respect to 100 parts by mass in total of the alkali-soluble resin (a) and the resin (b).

By containing the photoacid generator (c1), acid is generated in the light irradiation part, solubility in the alkali aqueous solution of the light irradiation part is increased, and a positive relief pattern in which the light irradiation part is dissolved can be obtained. In addition, by containing the photoacid generator (c1) and an epoxy compound or a thermal crosslinking agent described later, the acid generated in the light irradiation portion accelerates the crosslinking reaction of the epoxy compound or the thermal crosslinking agent, thereby obtaining a negative relief pattern in which the light irradiation portion is insoluble. I can. On the other hand, by containing a photoinitiator and a radical polymerizable compound to be described later, radical polymerization proceeds in the light irradiation portion, and a negative relief pattern in which the light irradiation portion becomes insoluble can be obtained.

As the photoacid generator (c1), a quinone diazide compound, a sulfonium salt, a phosphonium salt, a diazonium salt, an iodonium salt, etc. are mentioned, for example. It is preferable to contain two or more types of photoacid generators, and a highly sensitive photosensitive resin composition can be obtained. From the viewpoint of long-term reliability when the cured film of the present invention described later is used as the planarization layer and/or insulating layer of an organic EL display device, a quinonediazide compound is particularly preferable as the (c1) photoacid generator.

Examples of the quinonediazide compound include those in which a sulfonic acid of quinonediazide is ester-bonded to a polyhydroxy compound, a sulfonic acid of quinonediazide is sulfonamide bonded to a polyamino compound, and a sulfonic acid of quinonediazide is bonded to a polyhydroxypolyamino compound. These ester bonds and/or sulfonamide bonds, etc. are mentioned. It is preferable that 50 mol% or more of the total functional groups of these polyhydroxy compounds and polyamino compounds are substituted with sulfonic acids of quinonediazide.

As the quinone diazide structure, both a 5-naphthoquinone diazide sulfonyl group and a 4-naphthoquinone diazide sulfonyl group are preferably used. A naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group may be contained in the same molecule, and a 4-naphthoquinone diazide sulfonyl ester compound and You may contain a 5-naphthoquinone diazide sulfonyl ester compound. The 4-naphthoquinone diazide sulfonyl ester compound has absorption in the i-line region such as mercury, and is suitable for i-ray exposure. The 5-naphthoquinone diazide sulfonyl ester compound has an extended absorption to the g-line region of a mercury lamp, and is suitable for g-ray exposure.

It is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed, but from the viewpoint of high sensitivity, 4-naphthoquinone diazide sulfonyl ester It is preferred to include a compound. On the other hand, from the viewpoint of long-term reliability when the cured film of the present invention described later is used as a planarization layer and/or an insulating layer of an organic EL display device, a 5-naphthoquinone diazide sulfonyl ester compound is preferable. However, in the present invention, since long-term reliability can be improved by containing the above-described phenol resin (b) having a halogen atom, a 4-naphthoquinone diazide sulfonyl ester compound can be suitably used.

The quinone diazide compound can be synthesized from a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound by an arbitrary esterification reaction. By using these quinone diazide compounds, the resolution, sensitivity, and film residual rate are further improved.

Among the photoacid generators (c1), sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts are preferable because they appropriately stabilize the acid component generated by exposure. Among them, sulfonium salts are preferred. Further, a sensitizer or the like may be contained as necessary.

In the present invention, the content of the photoacid generator (c1) is preferably 0.1 parts by mass or more with respect to 100 parts by mass in total of the alkali-soluble resin (a) and the phenol resin (b) from the viewpoint of high sensitivity. It is preferably 10 parts by mass or more, and more preferably 25 parts by mass or more. From the viewpoint of further improving the chemical resistance of the cured film, 100 parts by mass or less is preferable. From the viewpoint of improving the long-term reliability when the cured film of the present invention described later is used as the planarization layer and/or insulating layer of an organic EL display device, the content of the photoacid generator (c1) is preferably small, but in the present invention, Since the long-term reliability can be improved by containing the above-described phenol resin (b) having a halogen atom, the content of the photo-acid generator (c1) can be increased for high sensitivity.

As a photoinitiator (c2), for example, a benzyl ketal photoinitiator, an α-hydroxyketone photoinitiator, an α-aminoketone photoinitiator, an acylphosphine oxide photoinitiator, an oxime ester photoinitiator, an acridine system A photoinitiator, a titanocene photoinitiator, a benzophenone photoinitiator, an acetophenone photoinitiator, an aromatic ketoester photoinitiator, a benzoic acid ester photoinitiator, etc. are mentioned. You may contain 2 or more types of photoinitiators (c2). From the viewpoint of further improving the sensitivity, an α-aminoketone type photoinitiator, an acylphosphine oxide type photoinitiator, and an oxime ester type photoinitiator are more preferable.

As an α-aminoketone type photoinitiator, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one, 3,6- Bis(2-methyl-2-morpholino propionyl)-9-octyl-9H-carbazole, and the like.

Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6- Dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide and the like.

Examples of the oxime ester photoinitiator include 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-me) Oxycarbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1, 2-dione-2-(O-benzoyl)oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[9 -Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-[2-methyl-4-[ 1-(2,2-dimethyl-1,3-dioxolan-4-yl)methyloxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime or 1-( 9-ethyl-6-nitro-9H-carbazol-3-yl)-1-[2-methyl-4-(1-methoxypropan-2-yloxy)phenyl]methanone-1-(O-acetyl ) Oxime and the like.

In the present invention, the content of the photopolymerization initiator (c2) is 0.1 parts by mass or more with respect to 100 parts by mass of the total of the alkali-soluble resin (a), the phenol resin (b) and the radical polymerizable compound described later from the viewpoint of high sensitivity. This is preferable, more preferably 1 part by mass or more, and still more preferably 10 parts by mass or more. On the other hand, from the viewpoint of further improving the resolution and reducing the taper angle, 50 parts by mass or less is preferable. From the viewpoint of improving the long-term reliability when the cured film of the present invention described later is used as the planarization layer and/or insulating layer of an organic EL display device, the content of the photoacid generator (c2) is preferably small, but in the present invention, Since the long-term reliability can be improved by containing the above-described phenol resin (b) having a halogen atom, it is possible to increase the content of the photoacid generator (c2) for high sensitivity.

<radical polymerizable compound>

The photosensitive resin composition of the present invention may further contain a radical polymerizable compound.

The radical polymerizable compound refers to a compound having a plurality of ethylenically unsaturated double bonds in a molecule. During exposure, radical polymerization of the radical polymerizable compound proceeds by radicals generated from the above-described photopolymerization initiator (c2), and the light irradiation portion becomes insoluble, thereby obtaining a negative pattern. Further, by containing the radical polymerizable compound, photocuring of the light irradiation portion is promoted, and the sensitivity can be further improved. In addition, since the crosslinking density after thermal curing is improved, the hardness of the cured film can be improved.

As the radical polymerizable compound, a compound having a (meth)acrylic group in which radical polymerization easily proceeds is preferable. From the viewpoint of improving the sensitivity at the time of exposure and improving the hardness of the cured film, a compound having two or more (meth)acrylic groups in the molecule is more preferable. As the double bond equivalent of the radical polymerizable compound, 80 to 400 g/mol is preferable from the viewpoint of improving the sensitivity at the time of exposure and improving the hardness of the cured film.

Examples of the radical polymerizable compound include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and pentaerythritol tri(meth)acrylate. , Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritolhepta(meth)acrylate, tripentaerythritol octa( Meth)acrylate, 2,2-bis[4-(3-(meth)acryloxy-2-hydroxypropoxy)phenyl]propane, 1,3,5-tris((meth)acryloxyethyl)isocyanate Nuric acid, 1,3-bis((meth)acryloxyethyl)isocyanuric acid, 9,9-bis[4-(2-(meth)acryloxyethoxy)phenyl]fluorene, 9,9-bis [4-(3-(meth)acryloxypropoxy)phenyl]fluorene, 9,9-bis(4-(meth)acryloxyphenyl)fluorene or their acid modified products, ethylene oxide modified products, propylene oxide And seed modified products.

In the resin composition of the present invention, the content of the radical polymerizable compound is 15 parts by mass per 100 parts by mass of the total of the alkali-soluble resin (a) and the radical polymerizable compound from the viewpoint of further improving the sensitivity and reducing the taper angle. Parts by mass or more are preferable, and 30 parts by mass or more are more preferable. On the other hand, from the viewpoint of further improving the heat resistance of the cured film and reducing the taper angle, 65 parts by mass or less are preferable, and 50 parts by mass or less are more preferable.

<Thermal crosslinking agent (d)>

The photosensitive resin composition of the present invention may further contain a thermal crosslinking agent (d). The thermal crosslinking agent (d) refers to a compound having at least two thermally reactive functional groups such as an alkoxymethyl group, a methylol group, an epoxy group, and an oxetanyl group in a molecule. By containing the thermal crosslinking agent (d), the alkali-soluble resin (a) or other additive components can be crosslinked to improve the heat resistance, chemical resistance, and bending resistance of the film after thermal curing.

As a preferred example of a compound having at least two alkoxymethyl groups or methylol groups, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP , DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP , DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE , TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, brand name, manufactured by Honshu Chemical Industry Co., Ltd.), "NIKALAC" (registered trademark) MX-290, "NIKALAC" MX-280, "NIKALAC" MX-270, "NIKALAC" MX-279, "NIKALAC" MW-100LM, "NIKALAC" MX-750LM (above, brand name, manufactured by Sanwa Chemical Co., Ltd.) Can be mentioned.

Preferred examples of the compound having at least two epoxy groups include "Epolite" (registered trademark) 40E, "Epolite" 100E, "Epolite" 200E, "Epolite" 400E, "Epolite" 70P, and "Epolite" 200P. , "Epolite" 400P, "Epolite" 1500NP, "Epolite" 80MF, "Epolite" 4000, "Epolite" 3002 (above, manufactured by Kyoesha Chemical Co., Ltd.), "Denacol" (registered) Trademark) EX-212L, "Denacol" EX-214L, "Denacol" EX-216L, "Denacol" EX-850L (above, manufactured by Nagase Chemtex Co., Ltd.), GAN, GOT (above, Nihon Kayaku Co., Ltd.), "Epicoat" (registered trademark) 828, "Epicoat" 1002, "Epicoat" 1750, "Epicoat" 1007, YX8100-BH30, E1256, E4250, E4275 (above, Japan epoxy resin ( Note) manufacturing), "Epiclon" (registered trademark) EXA-9583, HP4032 (above, manufactured by DIC Corporation), VG3101 (manufactured by Mitsui Chemical Co., Ltd.), "Tepic" (registered trademark) S, "Tepic "G, "Tepic" P (above, manufactured by Nissan Chemical Industry Co., Ltd.), "Denacol" EX-321L (manufactured by Nagase Chemtex Corporation), NC6000 (manufactured by Nihon Kayaku Corporation), "E Phototo" (registered trademark) YH-434L (manufactured by Toto Kasei Co., Ltd.), EPPN502H, NC3000 (manufactured by Nihon Kayaku Co., Ltd.), "Epiclon" (registered trademark) N695, HP7200 (above, DIC Corporation) Manufacturing) and the like.

Preferred examples of the compound having at least two oxetanyl groups include, for example, ethernacol EHO, ethernacol OXBP, ethernacol OXTP, ethernacol OXMA (manufactured by Ube Kosan Co., Ltd.), oxetanylated phenol novolac, etc. I can.

The thermal crosslinking agent (d) may be contained in combination of two or more.

The content of the thermal crosslinking agent (d) is preferably 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the total amount of the resin composition excluding the solvent. When the content of the thermal crosslinking agent (d) is 1 part by mass or more, the chemical resistance and bending resistance of the cured film can be further improved. In addition, when the content of the thermal crosslinking agent (d) is 30 parts by mass or less, the amount of outgas from the cured film can be further reduced, the long-term reliability of the organic EL display device can be further improved, and the storage stability of the resin composition is also excellent.

<solvent>

The photosensitive resin composition of the present invention may further contain a solvent. By containing a solvent, it can be made into the state of a varnish, and coatability can be improved.

As solvents, polar aprotic solvents such as γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, di Propylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tetrahydrofuran, ethers such as dioxane, acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2 -Ketones such as heptanone, 3-heptanone, and diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, esters such as ethyl lactate, 2-hydroxy-2-methyl ethyl propionate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3 -Ethoxy ethyl propionate, ethyl ethoxy acetate, ethyl hydroxyacetate, 2-hydroxy-3-methyl butanoate methyl, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl- 3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, Other esters such as n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, toluene, xylene, etc. Aromatic hydrocarbons, N-methylpi Rolidone, N,N-dimethylformamide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethyl Amides such as propanamide and N,N-dimethylisobutylamide, 3-methyl-2-oxazolidinone, and the like. You may contain 2 or more types of these.

The content of the solvent is not particularly limited, but is preferably 100 to 3000 parts by mass, and more preferably 150 to 2000 parts by mass based on 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent. In addition, the ratio of the solvent having a boiling point of 180° C. or higher to the total amount of the solvent is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less. By setting the ratio of the solvent having a boiling point of 180°C or higher to 20 parts by mass or less, the amount of outgas after heat curing can be further reduced, and the long-term reliability of the organic EL device can be further improved.

<Adhesion improver>

The photosensitive resin composition of the present invention may further contain an adhesion improving agent. As the adhesion improving agent, vinyl trimethoxysilane, vinyl triethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-sty Silane coupling agents such as riltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane, titanium chelate agents, aluminum chelate agents, A compound obtained by reacting an aromatic amine compound with an alkoxy group-containing silicon compound, etc. are mentioned. You may contain 2 or more types of these. By containing these adhesion-improving agents, it is possible to improve the development adhesion with underlying substrates such as _{silicon wafers, ITO, SiO 2, and silicon nitride in the case of developing a resin film or the like.} In addition, it is possible to increase the resistance to oxygen plasma and UV ozone treatment used for cleaning and the like. The content of the adhesion improving agent is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the resin composition excluding the solvent.

<Surfactant>

The photosensitive resin composition of the present invention may further contain a surfactant as necessary, and the wettability with the substrate can be improved. As surfactants, for example, Toray Dow Corning's SH series, SD series, ST series, Big Chemie Japan's BYK series, Shin-Etsu Chemical Co.'s KP series, Nichiyu's Disform series, "Megapak (registered trademark)" series of DIC Co., Ltd., Fluorad series of Sumitomo 3M Co., Ltd., "Sufflon (registered trademark)" series of Asahi Glass Co., Ltd., "Asahi Guard (Registered trademark)" series, fluorine-based surfactants such as Polyfox series of Omniba Solutions, Polyflow series of Kyoesha Chemical Co., Ltd., "Dispalon (registered trademark)" series of Kyusumoto Kasei Co., Ltd., etc. And acrylic and/or methacrylic surfactants.

The content of the surfactant is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the total amount of the resin composition excluding the solvent.

<Phenol compound having a phenolic hydroxyl group having a molecular weight of 100 or more and less than 500>

For the purpose of supplementing the alkali developability of the photosensitive resin composition of the present invention, a phenolic compound having a phenolic hydroxyl group having a molecular weight of 100 or more and less than 500 may be contained. As a phenolic compound having a phenolic hydroxyl group, for example, Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP- EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCRIPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO-BPA), TrisPHAP, TrisP-PA , TrisP-PHBA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T -OCHP, methylene tris-FR-CR, BisRS-26X, BisRS-OCHP (brand name, Honshu Chemical High School Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP -BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (above, brand name, Asahi Yukizai High School Co., Ltd.), 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-di Hydroxyquinoline, 2,6-dihydroxyquinoline, 2,3-dihydroxyquinoxaline, anthracene-1,2,10-triol, anthracene-1,8,9-triol, 8-quinolinol , Bisphenol A, bisphenol F, bisphenol Z, bisphenol E, bisphenol C, bisphenol G, bisphenol M, bisphenol P, bisphenol PH, bisphenol TMC, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2 ,4-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, 3,4, 5-trifluorophenol, 2,3,5,6-tetrafluorophenol, pentafluorophenol, 2,3,5,6-te Trafluoro-4-trifluoromethylphenol, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenol, perfluoro-1-naphthol, perfluoro-2-naphthol, 2- Chlorophenol, 3-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 2,6-dichlorophenol, 3,4-dichlorophenol, 3,5-dichlorophenol, 2,4,6-trichlorophenol , 3,4,5-trichlorophenol, 2,3,5,6-tetrachlorophenol, pentachlorophenol, 2,3,5,6-tetrachloro-4-trichloromethylphenol, 2,3,5 ,6-tetrachloro-4-pentachlorophenylphenol, perchloro-1-naphthol, perchloro-2-naphthol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2,4-di Bromophenol, 2,6-dibromophenol, 3,4-dibromophenol, 3,5-dibromophenol, 2,4,6-tribromophenol, 3,4,5-tribro Mophenol, 2,3,5,6-tetrabromophenol, pentabromophenol, 2,3,5,6-tetrabromo-4-tribromomethylphenol, 2,3,5,6-tetra Bromo-4-pentabromophenylphenol, perbromo-1-naphthol, perbromo-2-naphthol, 2-iodophenol, 3-iodophenol, 4-iodophenol, 2,4-diiodo Phenol, 2,6-diiodophenol, 3,4-diiodophenol, 3,5-diiodophenol, 2,4,6-triiodophenol, 3,4,5-triiodophenol , 2,3,5,6-tetraiodophenol, pentaiodophenol, 2,3,5,6-tetraiodo-4-triiodomethylphenol, 2,3,5,6-tetraiodo -4-pentaiodophenylphenol, periododo-1-naphthol, periododo-2-naphthol, 2-(trifluoromethyl)phenol, 3-(trifluoromethyl)phenol, 4-(trifluoro Romethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis (trifluoromethyl) phenol, 2,4,6-tris (trifluoromethyl) phenol, 2-cyano Phenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, Salicylic acid, methyl salicylate, bisphenol AF, bisphenol S, 2,2'-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 3,4- Dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2' And 4,4'-tetrahydroxybenzophenone. The photosensitive resin composition obtained by containing these compounds having a phenolic hydroxyl group is hardly soluble in an alkali developer before exposure, and is easily soluble in an alkali developer upon exposure, so that film reduction due to development is small, and development is possible in a short time. It becomes easier. Therefore, the sensitivity becomes easy to improve.

From the viewpoint of improving the long-term reliability when the cured film of the present invention described later is used as a planarization layer and/or an insulating layer of an organic EL display device, a phenolic compound having a phenolic hydroxyl group having a molecular weight of 100 or more and less than 500 further includes an electron withdrawing group. It is desirable to have.

_{In the present invention, the term "electron withdrawing group" is a group in which the value of the substituent constant σ p} ⁰ defined in the 5th edition II-379 to II-380 (Japanese Chemical Society Edition, published by Maruzen Co., Ltd.) is a positive group. to be. Specifically, a halogen atom, a cyano group, an oxy group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, a nitrile group, a nitro group, a sulfonyl group, a sulfinyl group, a halo(cyclo)alkyl group or a haloaryl group, and combinations thereof Can be lifted. In addition, a halo(cyclo)alkyl group refers to an alkyl group, a cycloalkyl group, and a haloaryl group in which at least a part is halogenated, and the aryl group in which at least part is halogenated.

As a specific example of a phenol compound (e) having an electron withdrawing group and a phenolic hydroxyl group having a molecular weight of 100 or more and less than 500, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,4-difluoro Phenol, 2,6-difluorophenol, 3,4-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol , 2,3,5,6-tetrafluorophenol, pentafluorophenol, 2,3,5,6-tetrafluoro-4-trifluoromethylphenol, 2,3,5,6-tetrafluoro -4-pentafluorophenylphenol, perfluoro-1-naphthol, perfluoro-2-naphthol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 2,6 -Dichlorophenol, 3,4-dichlorophenol, 3,5-dichlorophenol, 2,4,6-trichlorophenol, 3,4,5-trichlorophenol, 2,3,5,6-tetrachlorophenol, Pentachlorophenol, 2,3,5,6-tetrachloro-4-trichloromethylphenol, 2,3,5,6-tetrachloro-4-pentachlorophenylphenol, perchloro-1-naphthol, perchloro- 2-naphthol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2,4-dibromophenol, 2,6-dibromophenol, 3,4-dibromophenol, 3 ,5-dibromophenol, 2,4,6-tribromophenol, 3,4,5-tribromophenol, 2,3,5,6-tetrabromophenol, pentabromophenol, 2, 3,5,6-tetrabromo-4-tribromomethylphenol, 2,3,5,6-tetrabromo-4-pentabromophenylphenol, perbromo-1-naphthol, perbromo-2- Naphthol, 2-iodophenol, 3-iodophenol, 4-iodophenol, 2,4-diiodophenol, 2,6-diiodophenol, 3,4-diiodophenol, 3,5 -Diiodophenol, 2,4,6-triiodophenol, 3,4,5-triiodophenol, 2,3,5,6-tetraiodophenol, pentaiodophenol, 2,3, 5,6-tetraiodo-4-triiodomethylphenol, 2,3,5,6-tetraiodo-4-pentaiodophenylphenol, periododo-1-naphthol, periododo-2- Naphthol, 2-(trifluoromethyl)phenol, 3-(trifluoromethyl)phenol, 4-(trifluoromethyl)phenol, 2,6-bis(trifluoromethyl)phenol, 3,5-bi S(trifluoromethyl)phenol, 2,4,6-tris(trifluoromethyl)phenol, 2-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitro Phenol, 4-nitrophenol, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, salicylic acid, methyl salicylate, bisphenol AF, bisphenol S, 2,2'-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,4'- Trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, etc., and these may be used alone or as a mixture thereof. Can be used.

From the viewpoint of the heat resistance of the phenolic hydroxyl group having a phenolic hydroxyl group, bisphenols are preferred as the phenolic compound (e) having an electron withdrawing group and a phenolic hydroxyl group having a molecular weight of 100 or more and less than 500. As bisphenols, bisphenol AF, bisphenol S, 2,2'-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 3,4-dihydroxybenzo Phenone, 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4 '-Tetrahydroxybenzophenone, etc. are mentioned.

The content of the phenolic compound having a phenolic hydroxyl group having a molecular weight of 100 or more and less than 500 is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of (a) alkali-soluble resin. By setting it as the above-mentioned range, after maintaining high heat resistance, alkali developability of a photosensitive resin composition can be improved.

<Inorganic particles>

The photosensitive resin composition of the present invention may further contain inorganic particles. As a preferable specific example of an inorganic particle, silicon oxide, titanium oxide, barium titanate, alumina, talc, etc. are mentioned, for example. The primary particle diameter of the inorganic particles is preferably 100 nm or less, and more preferably 60 nm or less.

The content of the inorganic particles is preferably 5 to 90 parts by mass with respect to 100 parts by mass of the total amount of the resin composition excluding the solvent.

<Thermal acid generator>

The photosensitive resin composition of the present invention may further contain a thermal acid generator within a range that does not impair the long-term reliability of the organic EL display device. The thermal acid generator generates acid by heating to accelerate the crosslinking reaction of the thermal crosslinking agent. In addition, when the resin of component (a) has an unopened imide ring structure or an oxazole ring structure, it promotes their cyclization. So that the mechanical properties of the cured film can be further improved.

The thermal decomposition start temperature of the thermal acid generator used in the present invention is preferably 50°C to 270°C, and more preferably 250°C or less. In addition, when drying (pre-baking: about 70 to 140°C) after applying the resin composition of the present invention to a substrate, acid is not generated, and final heating after patterning in subsequent exposure and development (cure: about 100 to 400 °C) is preferable because it is possible to suppress a decrease in sensitivity during development.

The acid generated from the thermal acid generator used in the present invention is preferably a strong acid, for example, arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, and other alkylsulfonic acids or trifluoro. Haloalkylsulfonic acids, such as romethylsulfonic acid, etc. are preferable. These are used as a salt such as an onium salt or as a covalent compound such as imide sulfonate. You may contain 2 or more types of these.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the total amount of the resin composition excluding the solvent. By containing 0.01 parts by mass or more of the thermal acid generator, since the crosslinking reaction and the cyclization of the unopened structure of the resin are promoted, the mechanical properties and chemical resistance of the cured film can be further improved. Further, from the viewpoint of long-term reliability of the organic EL display device, 5 parts by mass or less are preferable, and 2 parts by mass or less are more preferable.

<Production method of photosensitive resin composition>

Next, a method for producing the photosensitive resin composition of the present invention will be described. For example, alkali-soluble resins (a), phenolic resins (b) and photosensitive compounds (c), and if necessary, radical polymerizable compounds, thermal crosslinking agents, solvents, adhesion improvers, surfactants, phenols having a molecular weight of 100 or more and less than 500 A photosensitive resin composition can be obtained by dissolving a phenolic compound having a hydroxyl group, an inorganic particle, a thermal acid generator, and the like.

Stirring and heating are mentioned as a dissolution method. In the case of heating, the heating temperature is preferably set within a range that does not impair the performance of the photosensitive resin composition, and is usually from room temperature to 80°C. In addition, the dissolution order of each component is not particularly limited, and for example, a method of sequentially dissolving a compound having low solubility is exemplified. In addition, for components that tend to generate bubbles during stirring and dissolution, such as surfactants and some adhesion improvers, by adding the other components last after dissolving, it is possible to prevent poor dissolution of other components due to the generation of bubbles. .

It is preferable that the obtained photosensitive resin composition is filtered using a filtration filter to remove dust and particles. Filter pore diameters include, for example, 0.5 µm, 0.2 µm, 0.1 µm, 0.07 µm, 0.05 µm, and 0.02 µm, but are not limited thereto. The material of the filtration filter includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), and the like, and polyethylene or nylon is preferable.

<Photosensitive resin sheet>

The photosensitive resin sheet of the present invention is formed using the photosensitive resin composition.

The sheet of the present invention can be obtained by applying the above-described photosensitive resin composition on a peelable substrate such as polyethylene terephthalate to obtain a coating film of the photosensitive resin composition and drying it. You may laminate a protective film further.

As an application method, a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method, etc. are mentioned, for example. Among these, the slit coating method is preferred because it can be applied with a small amount of the coating liquid and is advantageous for cost reduction. The amount of the coating liquid required for the slit coating method is, for example, about 1/5 to 1/10 compared to the spin coating method. As a slit nozzle used for coating, for example, Dai Nippon Screen Seizou Co., Ltd. ``Linear Coater'', Tokyo Oka Kogyo Co., Ltd. ``Spinless'', Toray Engineering Co., Ltd. ``TS Coater'', and Zugairo "Table Coater" manufactured by Kogyo Corporation, "CS Series" "CL Series" manufactured by Tokyo Electron, "In-Line Slit Coater" manufactured by Thermotronics Boeki Corporation, "Head Coater" manufactured by Hirata Kiko Corporation HC series” and other products available from multiple manufacturers can be selected. The coating speed is generally in the range of 10 mm/sec to 400 mm/sec. The film thickness of the coating film varies depending on the solid content concentration and viscosity of the resin composition, but is usually applied so that the film thickness after drying is 0.1 to 10 µm, preferably 0.3 to 5 µm.

Prior to application, the substrate to which the photosensitive resin composition is applied may be pretreated with the above-described adhesion improving agent. As a pretreatment method, for example, 0.5 to 20 mass of an adhesion improving agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. A method of treating the substrate surface using a solution dissolved in% is mentioned. Examples of the treatment method of the substrate surface include a spin coating method, a slit die coating method, a bar coating method, a dip coating method, a spray coating method, and a vapor treatment method.

After application, it is common to perform a vacuum drying treatment as necessary to heat-dry the coating film. This process is also called prebaking. For drying, use a hot plate, oven, or infrared light. In the case of using a hot plate, the coating film is held and heated directly on the plate or on a jig such as a proxy pin installed on the plate. Examples of the material of the proxy pin include metal materials such as aluminum and stainless steel, and synthetic resins such as polyimide resin and "Teflon" (registered trademark). Any material of proxy pin can be used as long as it is heat-resistant. The height of the proxy pin varies depending on the size of the substrate, the type of the coating film, the purpose of heating, and the like, but is preferably about 0.1 to 10 mm. The heating temperature and heating time vary depending on the type and purpose of the coating film, but the heating temperature is preferably 50° C. to 180° C., and the heating time is preferably 1 minute to several hours.

The photosensitive resin sheet can form a pattern. For example, a desired pattern can be formed by exposing the photosensitive resin sheet to exposure by irradiating actinic rays through a mask having a desired pattern and developing it.

Examples of actinic rays used for exposure include ultraviolet rays, visible rays, electron rays, and X rays. In the present invention, it is preferable to use i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp. In the case of having a positive photosensitive property, the exposed portion is dissolved in the developer. In the case of having negative photosensitivity, the exposed portion is cured and insoluble in a developer.

After exposure, a desired pattern is formed by removing the exposed portion in the case of the positive type and the non-exposed portion in the case of the negative type with a developer. As a developer, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethyl An aqueous solution of an alkaline compound such as aminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine is preferable. To these aqueous alkali solutions, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol , Alcohols such as ethanol and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added. . Examples of the developing method include methods such as spray, puddle, immersion, and ultrasonic waves.

Next, it is preferable to rinse the pattern formed by development with distilled water. Alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to distilled water and rinsed.

<cured film>

The cured film of the present invention can be obtained by curing the photosensitive resin sheet or photosensitive resin composition. Since the component having low heat resistance can be removed by heat-curing the above-described photosensitive resin composition or photosensitive resin sheet, heat resistance and chemical resistance can be further improved. In particular, when the photosensitive resin composition or the photosensitive resin sheet of the present invention contains a polyimide precursor, a polybenzoxazole precursor, a copolymer thereof, or a copolymer of them and a polyimide, an imide ring or an oxazole ring Thus, it is possible to further improve heat resistance and chemical resistance.

The heating curing temperature is preferably 180°C or higher, more preferably 200°C or higher, still more preferably 230°C or higher, and particularly preferably 250°C or higher from the viewpoint of further reducing the amount of outgas generated from the cured film. On the other hand, from the viewpoint of improving the film toughness of the cured film, 500°C or less is preferable, and 450°C or less is more preferable. In this temperature range, the temperature may be raised step by step, or the temperature may be continuously raised. The heating curing time is preferably 30 minutes or longer from the viewpoint of further reducing the amount of outgas. Moreover, 3 hours or less is preferable from a viewpoint of improving the film toughness of a cured film. For example, a method of performing heat treatment at 150° C. and 250° C. for 30 minutes each, or a method of performing heat treatment while linearly raising the temperature from room temperature to 300° C. over 2 hours may be mentioned.

The photosensitive resin composition, photosensitive resin sheet, and cured film of the present invention include a surface protective layer or an interlayer insulating layer of a semiconductor device, an insulating layer of an organic electroluminescence (hereinafter referred to as EL) device, and a display using an organic EL device. Thin Film Transistor for driving devices (Thin Film Transistor: hereinafter referred to as TFT) Suitable for flattening layers on boards, wiring protection insulating layers on circuit boards, on-chip microlenses for solid-state imaging devices, and flattening layers for various displays and solid-state imaging devices. Is used. For example, it is suitable as a surface protection layer or interlayer insulating layer such as MRAM with low heat resistance, polymer ferroelectric RAM (PFRAM), phase change memory (Phase Change RAM: PCRAM, Ovonics Unified Memory: OUM), which are promising as next-generation memory. Do. In addition, a display device including a first electrode formed on a substrate and a second electrode provided opposite to the first electrode, for example, an LCD, ECD, ELD, a display device using an organic electroluminescent element (organic electroluminescent device ) Can also be used for insulating layers. Hereinafter, an organic EL display device, a semiconductor device, and a semiconductor electronic component will be described as an example.

<Organic EL display device>

The cured film of the present invention can be suitably used for a planarizing layer and/or an insulating layer in an organic EL display device having a driving circuit, a planarizing layer, a first electrode, an insulating layer, a light emitting layer, and a second electrode on a substrate. . Organic light-emitting materials are generally weak to gas components or moisture, and when exposed to them, light emission luminance decreases and pixel shrinkage occurs. Here, the pixel shrink refers to a phenomenon in which the light emission luminance decreases or does not light up from the end of the pixel. Long-term reliability can be improved by including the cured film of the present invention as a planarization layer and/or an insulating layer of an organic EL display device. In particular, since the insulating layer is adjacent to the organic light-emitting material, the effect on long-term reliability is greater than that of the planarization layer, and in order to obtain an organic EL display device having high long-term reliability, it is preferable to include at least the cured film of the present invention in the insulating layer.

For example, an active matrix type display device has a TFT on a substrate such as glass or various plastics, and has a wiring connected to the TFT located on the side of the TFT, and has a planarization layer so as to cover the irregularities thereon. A display element is provided on the planarization layer. The display element and the wiring are connected through a contact hole formed in the planarization layer. In particular, in recent years, flexibility of organic EL display devices has become mainstream, and it is preferable that the substrate having the above-described driving circuit is an organic EL display device containing a resin film. When the photosensitive resin composition of the present invention or the cured film obtained by curing the photosensitive sheet is used as an insulating layer and a planarizing layer of such a flexible display, it is particularly preferably used because it has excellent bending resistance. From the viewpoint of improving the adhesiveness with the photosensitive resin composition of the present invention or the cured film obtained by curing the photosensitive sheet, polyimide is particularly preferred as the resin film.

When the cured film of the present invention is used as the planarization layer, the film thickness is preferably 1.0 to 5.0 µm, more preferably 2.0 µm or more. By making the planarization layer within the above-described range, it is possible to improve the flatness of densely packed TFTs and wirings due to high definition. When the planarization layer is thickened, the outgas increases and the long-term reliability of the organic EL display device is deteriorated. However, even when the cured film of the present invention is thickened, the long-term reliability can be improved. Further, for high definition, the planarization layer is preferably multilayered in that TFTs and wirings can be arranged in the film thickness direction as well. The number of layers is, for example, 2 to 5 layers.

The organic EL display device of the present invention preferably has a portion in which at least a portion of the portion provided with the cured film is bent and/or a portion fixed in a bent state. An organic EL display device excellent in bending resistance can be obtained by using the photosensitive resin composition of the present invention or a cured film obtained by curing the photosensitive resin sheet. The radius of curvature of the above-described bendable portion and/or the portion fixed in the bent state is preferably 0.1 mm or more, and preferably 5 mm or less. When the radius of curvature is 0.1 mm or more, bending resistance in the bent portion can be ensured, and when it is 5 mm or less, design properties such as narrowing of the frame width can be ensured. The organic EL display device of the present invention can be bent at any suitable portion. For example, the organic EL display device may be bent at the center portion like a foldable display device, or may be bent at the end from the viewpoint of securing the design and the display screen to the maximum. In addition, the organic EL display device may be bent along its longitudinal direction or may be bent along its short direction. Depending on the application, a specific portion of the organic EL display device may be bent (for example, some or all of the four corners may be bent in an oblique direction).

1 is a cross-sectional view of an example of a TFT substrate. On the substrate 6, a bottom-gate or top-gate TFT (thin film transistor) 1 is provided in a matrix, and a TFT insulating layer 3 is formed in a state covering the TFT 1. Further, a wiring 2 connected to the TFT 1 is provided on the TFT insulating layer 3. Further, on the TFT insulating layer 3, a planarization layer 4 is provided in a state in which the wiring 2 is embedded. In the planarization layer 4, a contact hole 7 reaching the wiring 2 is provided. Then, an ITO (transparent electrode) 5 is formed on the planarization layer 4 in a state connected to the wiring 2 through the contact hole 7. Here, the ITO 5 becomes an electrode of a display element (for example, an organic EL element). In addition, an insulating layer 8 is formed to cover the periphery of the ITO 5. The organic EL element may be of a top emission type that emits light from the side opposite to the substrate 6 or a bottom emission type that extracts light from the side of the substrate 6. In this way, an active matrix type organic EL display device in which the TFT 1 for driving the respective organic EL elements is connected is obtained.

The TFT insulating layer 3, the planarization layer 4 and/or the insulating layer 8 is a step of forming a photosensitive resin film comprising the photosensitive resin composition or photosensitive resin sheet of the present invention as described above, the photosensitive resin It can form by a process of exposing a film, a process of developing an exposed photosensitive resin film, and a process of heat-processing the developed photosensitive resin film. An organic EL display device can be obtained from a manufacturing method having these steps.

<Semiconductor electronic component, semiconductor device>

The cured film of the present invention can be suitably used for an electrode, a metal wiring, an interlayer insulating layer and/or a surface protective layer in a semiconductor electronic component and a semiconductor device having an electrode, a metal wiring, an interlayer insulating layer and/or a surface protective layer on a substrate. . The cured film of the present invention may be included in at least a part of the interlayer insulating layer and/or the surface protective layer. Since the cured film of the present invention is excellent in mechanical properties, it is possible to relieve stress from the sealing resin even during mounting, suppress damage to the low-k layer, and provide a highly reliable semiconductor device.

2 is an enlarged cross-sectional view of an example of a pad portion of a semiconductor device having bumps. On the silicon wafer 9, an Al pad 10 for input/output and a passivation layer 11 having via holes are formed. In addition, an insulating layer 12 is formed on the passivation layer 11, and a metal layer 13 containing Cr, Ti, etc. is formed to be connected to the Al pad 10, and Al, Cu, etc. are formed by electrolytic plating or the like. A metal wiring 14 including a is formed. By etching the metal layer 13 located around the solder bumps 18, the pads are insulated from each other. A barrier metal 16 and a solder bump 18 are formed on the insulated pad. When processing the insulating film 15, a scribe line 17 is formed.

Next, a method of manufacturing a semiconductor device will be described with reference to the drawings. 3 shows an example of a method for manufacturing a semiconductor device having bumps. In the step 3a, the resin composition of the present invention is applied on the silicon wafer 9 on which the Al pad 10 and the passivation layer 11 are formed, and the patterned insulating layer 12 is formed through a photolithography process. do. Next, in step 3b, the metal layer 13 is formed by sputtering. In step 3c, a metal wiring 14 is formed on the metal layer 13 by a plating method. Next, in the step 3d', the resin composition of the present invention is applied, and in the step 3d, a pattern of the insulating layer 15 is formed through a photolithography step. At this time, the resin composition constituting the insulating layer 15 is processed into a thick film in the scribe line 17. An additional wiring (so-called redistribution) may be formed on the insulating layer 15. In the case of forming a multilayer wiring structure of two or more layers, by repeatedly performing the above-described process, a multilayer wiring structure in which two or more rewiring layers are separated by an interlayer insulating layer containing the cured film of the present invention can be formed. . Although there is no upper limit on the number of layers in the multilayer wiring structure, those with 10 or less layers are often used. Next, in step 3e, the barrier metal 16 is formed, and in step 3f, the solder bump 18 is formed. Then, it is diced along the last scribe line 17 and cut out for each chip, thereby obtaining a semiconductor device having bumps.

Example

Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited by these examples. In addition, each evaluation in Examples was performed by the following method.

(1) sensitivity

The varnish obtained by each Example and Comparative Example was applied by spin coating on an 8-inch silicon wafer using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Co., Ltd.), and baked at 120° C. for 3 minutes. To prepare a prebaked film having a thickness of 3.0 µm. In addition, the film thickness was measured under the conditions of a refractive index of 1.63 using Lambda Ace STM-602 manufactured by Dai Nippon Screen Seizou Co., Ltd. Thereafter, exposure was performed every 5 mJ/cm 2 in a range of 50 to 300 mJ/cm 2 through a mask having a contact hole pattern of 10 µm using an exposure machine i-line stepper NSR-2005i9C (manufactured by Nikon Corporation). After exposure, using the developing device of ACT-8, 2.38% by weight of tetramethylammonium aqueous solution (hereinafter TMAH, manufactured by Tama Chemical Industry Co., Ltd.) was used as a developer and developed until the film reduction amount became 0.5 μm. After performing, it rinsed with distilled water, shaken and dried, and the pattern was obtained.

The obtained pattern was observed at 20 times magnification using an FDP microscope MX61 (manufactured by Olympus Co., Ltd.), and the opening diameter of the contact hole was measured. The minimum exposure amount at which the opening diameter of the contact hole reached 10 µm was determined, and this was taken as the sensitivity.

(2) Bending tolerance evaluation

As shown in Fig. 5, the varnish obtained by each Example and Comparative Example was applied on a polyimide film substrate 25 having a film thickness of 20 μm at an arbitrary number of rotations by spin coating to obtain a photosensitive resin film. , As a drying process, it prebaked for 2 minutes on a 120 degreeC hot plate, and obtained the photosensitive resin film. Next, it was developed by showering for 90 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution using an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.), and then rinsed with pure water for 30 seconds. Using an inner oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the substrate with the developed photosensitive resin film was heated while raising the temperature to 250°C under a temperature increase condition of 5°C/min at an oxygen concentration of 20 ppm or less. Then, baking was performed at 250° C. for 1 hour to obtain a cured film 26 having a thickness of 2.0 µm.

Subsequently, ten polyimide film substrates 25 provided with a cured film were cut out into a size of 50 mm in length x 10 mm in width. Next, the surface of the cured film 26 was turned to the outside, and the polyimide film substrate 25 was held for 30 seconds in a state in which the polyimide film substrate 25 was bent at 180° on a 25 mm long line. After 30 seconds, the bent polyimide film substrate was unfolded, and using an FPD inspection microscope (MX-61L; manufactured by Olympus Co., Ltd.), a bent portion on a line having a length of 25 mm on the surface of the cured film was observed, and the surface of the cured film was The appearance change was evaluated. The bending test was performed in the range of a radius of curvature of 0.1 to 1.0 mm, and the minimum radius of curvature at which no change in appearance such as cracks or other appearance changes occurred on the surface of the cured film or peeling of the cured film from the polyimide film substrate was recorded.

(3) Long-term reliability evaluation of organic EL display devices

4 is a schematic diagram of a manufacturing procedure of an organic EL display device. First, a 10 nm ITO transparent conductive film was formed on the entire surface of the substrate by a sputtering method on an alkali-free glass substrate 19 of 38 mm mm x 46 mm, and etched as the first electrode (transparent electrode) 20. At the same time, an auxiliary electrode 21 for taking out the second electrode was also formed. The obtained substrate was ultrasonically cleaned for 10 minutes with SemicoClean 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.), and then washed with ultrapure water. Next, the photosensitive resin composition shown in Table 1 was applied to the entire surface of the substrate by spin coating, and prebaked on a hot plate at 120° C. for 2 minutes. After UV exposure to this film through a photomask, it was developed with a 2.38 mass% TMAH aqueous solution to dissolve an unnecessary portion, and rinsed with pure water. The obtained resin pattern was heat-treated at 250° C. for 1 hour in a nitrogen atmosphere using an inner oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.). In this way, an insulating layer 22 having a shape in which openings having a width of 70 μm and a length of 260 μm are arranged at a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction, and each opening exposes the first electrode, It was formed only in the substrate effective area. In this way, an insulating layer having an opening ratio of the insulating layer 25% was formed in the effective area of the substrate having a square of 16 mm on one side. The thickness of the insulating layer was about 1.0 μm.

Next, after carrying out nitrogen plasma treatment as a pretreatment, an organic EL layer 23 including a light emitting layer was formed by a vacuum evaporation method. In addition, the degree of vacuum during evaporation was 1×10 ⁻³ Pa or less, and the substrate was rotated with respect to the evaporation source during evaporation. First, 10 nm of compound (HT-1) was deposited as a hole injection layer, and 50 nm of compound (HT-2) was deposited as a hole transport layer. Next, a compound (GH-1) as a host material and a compound (GD-1) as a dopant material were deposited on the light-emitting layer to a thickness of 40 nm with a doping concentration of 10%. Next, compound (ET-1) and compound (LiQ) as electron transport materials were laminated to a thickness of 40 nm at a volume ratio of 1:1. The structure of the compound used in the organic EL layer is shown below.

Next, 2 nm of compound (LiQ) was deposited, and then Mg and Ag were deposited at 10 nm in a volume ratio of 10:1 to obtain a second electrode (non-transparent electrode) 24. Finally, the cap-shaped glass plate was sealed by bonding it with an epoxy resin-based adhesive in a low-humidity nitrogen atmosphere, and four top emission organic EL display devices having a square of 5 mm on one side were fabricated on one substrate. In addition, the film thickness here is a display value in a crystal oscillation type film thickness monitor.

The prepared organic EL display device was placed on a hot plate heated to 80° C. with the light emitting surface facing up, and was irradiated with UV light having a wavelength of 365 nm and an illuminance of 0.6 mW/cm 2. Immediately after irradiation (0 hours), 250 hours, 500 hours, and 1000 hours, the organic EL display device is made to emit light by direct current driving of 0.625 mA, and the area ratio of the light-emitting portion to the area of the light-emitting pixel (pixel emission area ratio) is measured. I did. As the pixel emission area ratio after 1000 hours elapsed by this evaluation method, it can be said that long-term reliability is excellent if it is 80% or more, and it is more preferable if it is 90% or more.

(4) Measurement of the weight average molecular weight of the phenol resin

With respect to the resins obtained by Synthesis Examples 8 to 15 and Comparative Synthesis Examples 1 to 2, using a GPC (gel permeation chromatography) apparatus Waters2690-996 (manufactured by Nippon Waters Co., Ltd.), the developing solvent was N-methyl- Using 2-pyrrolidone (hereinafter referred to as NMP), the weight average molecular weight (Mw) in terms of polystyrene was measured.

Synthesis Example 1 Synthesis of a hydroxyl group-containing diamine compound (α)

2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) 18.3 g (0.05 mol) was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide,- Cooled to 15°C. A solution in which 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride was dissolved in 100 mL of acetone was added dropwise thereto. After completion of the dropwise addition, it was made to react at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was separated by filtration and vacuum dried at 50°C.

30 g of solid was put in a 300 mL stainless steel autoclave, dispersed in 250 mL of methylcellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here by a balloon, and a reduction reaction was carried out at room temperature. After about 2 hours, it was confirmed that the balloon no longer shrunk and the reaction was terminated. After the reaction was completed, the palladium compound as a catalyst was removed by filtration, and concentrated in a rotary evaporator to obtain a hydroxyl group-containing diamine compound (?) represented by the following formula.

Synthesis Example 2 Synthesis of quinonediazide compound (c-1)

Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of 5-naphthoquinone diazide sulfonyl acid chloride were added to 1,4-dioxane. It dissolved in 450 g, and it was set to room temperature. Here, 50 g of 1,4-dioxane and 15.18 g of mixed triethylamine were added dropwise so that the inside of the system would not be 35°C or higher. After dripping, it stirred at 30 degreeC for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Then, the precipitated precipitate was collected by filtration. This precipitate was dried in a vacuum dryer to obtain a quinone diazide compound (c-1) represented by the following formula.

Synthesis Example 3 Synthesis of quinonediazide compound (c-2)

Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of 4-naphthoquinone diazide sulfonyl acid chloride were added to 1,4-dioxane. It dissolved in 450 g, and it was set to room temperature. Here, 50 g of 1,4-dioxane and 15.18 g of mixed triethylamine were added dropwise so that the inside of the system would not be 35°C or higher. After dripping, it stirred at 30 degreeC for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Then, the precipitated precipitate was collected by filtration. This precipitate was dried in a vacuum dryer to obtain a quinone diazide compound (c-2) represented by the following formula.

Synthesis Example 4 Synthesis of alkali-soluble resin (a-1)

Under a stream of dry nitrogen, 31.0 g (0.10 mol) of 3,3',4,4'-diphenylethertetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of NMP. Here, 45.35 g (0.075 mol) of the hydroxyl group-containing diamine compound (α) obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane (hereinafter referred to as SiDA) Was added together with 50 g of NMP, and reacted at 40° C. for 2 hours. Next, 4.36 g (0.04 mol) of 3-aminophenol (hereinafter referred to as MAP) as an end sealant was added together with 5 g of NMP, and reacted at 50° C. for 2 hours. Then, a solution obtained by diluting 32.39 g (0.22 mol) of N,N-dimethylformamide diethylacetal with 50 g of NMP was added dropwise over 10 minutes. After dripping, it stirred at 50 degreeC for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain a polyimide precursor (a-1) as an alkali-soluble resin.

Synthesis Example 5 Synthesis of alkali-soluble resin (a-2)

Under a dry nitrogen stream, BAHF 29.3 g (0.08 mol), SiDA 1.24 g (0.005 mol), and MAP 3.27 g (0.03 mol) as an end sealant were dissolved in NMP 150 g. To this, 31.0 g (0.1 mol) of 3,3',4,4'-diphenylethertetracarboxylic dianhydride (hereinafter referred to as ODPA) was added together with 50 g of NMP, followed by stirring at 20°C for 1 hour, and then The mixture was stirred at 50° C. for 4 hours. Thereafter, 15 g of xylene was added, followed by stirring at 150°C for 5 hours while azeotropically boiling water with xylene. After the stirring was completed, the solution was added to 3L of water to collect white precipitates. This precipitate was collected by filtration, washed three times with water, and dried in a vacuum dryer at 80°C for 24 hours to obtain polyimide (a-2) as an alkali-soluble resin.

Synthesis Example 6 Synthesis of alkali-soluble resin (a-3)

Under a dry nitrogen stream, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether, and the temperature of the solution was cooled to -15°C. Here, 7.4 g (0.025 mol) of diphenyl ether dicarboxylic acid dichloride (manufactured by Nihon Noyaku Co., Ltd.), 5.1 g (0.025 mol) of isophthalic acid chloride (manufactured by Tokyo Kasei Co., Ltd.) were added to γ-butyrolactone ( The solution dissolved in 25 g of GBL) was added dropwise so that the internal temperature did not exceed 0°C. After completion of the dropwise addition, stirring was continued at -15°C for 6 hours. After completion of the reaction, a solution was added to 3L of water containing 10% by weight of methanol to collect white precipitates. This precipitate was collected by filtration, washed three times with water, and dried in a vacuum dryer at 80° C. for 24 hours to obtain a polybenzoxazole precursor (a-3) as an alkali-soluble resin.

Synthesis Example 7 Synthesis of alkali-soluble resin (a-4)

In a 500 ml flask, 5 g of 2,2'-azobis (isobutyronitrile), 5 g of t-dodecanethiol, and 150 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) were added. Thereafter, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo[5.2.1.0 ^2,6 ]decane-8-ylmethacrylate were added, followed by stirring at room temperature for a while, and nitrogen substitution in the flask. Then, it heated and stirred at 70 degreeC for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, and 0.2 g of p-methoxyphenol were added to the obtained solution, followed by heating and stirring at 90° C. for 4 hours to obtain an acrylic resin (a- A solution of 4) was obtained. The solid content concentration of the obtained acrylic resin solution was 43% by weight.

Synthesis Example 8 Synthesis of a phenol resin (b-1) having a halogen atom

Under a dry nitrogen stream, 672 g (2.0 mol) of bisphenol AF and 96 g (1.6 mol) of 50 wt% formaldehyde aqueous solution were dissolved in 250 g of methyl isobutyl ketone, and 2.5 g of p-toluenesulfonic acid was added while cooling to 30° C. or less, The mixture was stirred at 100°C for 4 hours. After the stirring was completed, 5.3 g of a 10% NaOH aqueous solution was added, and after neutralization, washing was performed with 750 g of pure water in order to remove the neutralized salt. Subsequently, it heated up for 2 hours while concentrating to 160 degreeC, and dried under reduced pressure for 30 minutes at 160 degreeC and 100 mmHg, and the novolac resin (b-1) of bisphenol AF was obtained. The weight average molecular weight of (b-1) was 1300.

Synthesis Example 9 Synthesis of a phenol resin (b-2) having a halogen atom

Bisphenol AF-cresol novolac resin (b-2) was obtained in the same manner as in Synthesis Example 8 except that bisphenol AF 537 g (1.6 mol) and m-cresol 43 g (0.4 mol) were used instead of bisphenol AF 672 g (2.0 mol). . The weight average molecular weight of (b-2) was 1200.

Synthesis Example 10 Synthesis of a phenol resin (b-3) having a halogen atom

Bisphenol AF-cresol novolac resin (b-3) was obtained in the same manner as in Synthesis Example 8, except that 336 g (1.0 mol) of bisphenol AF and 108 g (1.0 mol) of m-cresol were used instead of 672 g (2.0 mol) of bisphenol AF. . The weight average molecular weight of (b-3) was 1100.

Synthesis Example 11 Synthesis of a phenol resin (b-4) having a halogen atom

Bisphenol AF-cresol novolac resin (b-4) was obtained in the same manner as in Synthesis Example 8 except that 134 g (0.4 mol) of bisphenol AF and 173 g (1.6 mol) of m-cresol were used instead of 672 g (2.0 mol) of bisphenol AF. . The weight average molecular weight of (b-4) was 1000.

Synthesis Example 12 Synthesis of a phenol resin (b-5) having a halogen atom

A novolac resin (b-5) of bisphenol AF was obtained in the same manner as in Synthesis Example 8 except that 170 g (1.6 mol) of benzaldehyde was used instead of 96 g (1.6 mol) of a 50% by weight formaldehyde aqueous solution. The weight average molecular weight of (b-5) was 1400.

Synthesis Example 13 Synthesis of a phenol resin (b-6) having a halogen atom

Dissolve 672 g (2.0 mol) of bisphenol AF and 240 g (4.0 mol) of 50 wt% formaldehyde aqueous solution in 250 g of methylisobutyl ketone in a 4-neck flask equipped with a stirrer, cooling tube, dropping funnel, and thermometer, and cooled to 30°C or less While adding 6.4 g of trimethylamine, it stirred at 100 degreeC for 2 hours. After completion of the stirring, 4 parts of oxalic acid was added, followed by drying under reduced pressure at 100°C and 400 mmHg for 2 hours to obtain a resol resin (b-6) of bisphenol AF. The weight average molecular weight of (b-6) was 900.

Synthesis Example 14 Synthesis of a phenol resin (b-8) having a halogen atom

Bisphenol AF/bisphenol S novolac resin (b-8) was obtained in the same manner as in Synthesis Example 8 except that bisphenol AF 537 g (1.6 mol) and bisphenol S 100 g (0.4 mol) were used instead of bisphenol AF 672 g (2.0 mol). . The weight average molecular weight of (b-8) was 1300.

Synthesis Example 15 Synthesis of a phenol resin (b-9) having a halogen atom

Bisphenol AF/bisphenol A novolac resin (b-9) was obtained in the same manner as in Synthesis Example 8 except that bisphenol AF 537 g (1.6 mol) and bisphenol A 91 g (0.4 mol) were used instead of bisphenol AF 672 g (2.0 mol). . The weight average molecular weight of (b-9) was 1200.

Comparative Synthesis Example 1 Synthesis of a phenol resin (b'-1) having no halogen atom

In a dry nitrogen stream, 456 g (2.0 mol) of bisphenol A, 84 g (1.4 mol) of a 50% by weight formaldehyde aqueous solution, and 250 g of methyl isobutyl ketone were mixed, and 4.6 g of oxalic acid was added while cooling to 30° C. or lower, and then at 100° C. It was stirred for 4 hours. After completion of the stirring, the mixture was heated for 2 hours while concentrating to 160°C, and dried under reduced pressure at 160°C and 100 mmHg for 30 minutes to obtain a bisphenol A novolac resin (b'-1). The weight average molecular weight of (b'-1) was 900.

Comparative Synthesis Example 2 Synthesis of a phenol resin (b'-2) having no halogen atom

Under a dry nitrogen stream, m-cresol 70.2 g (0.65 mol), p-cresol 37.8 g (0.35 mol), 50 wt% formaldehyde aqueous solution 56 g (0.93 mol), oxalic acid dihydrate 0.63 g (0.005 mol), methyl isobutyl After 260 g of ketones were put into a 500 ml flask, the flask was immersed in an oil bath, and the reaction solution was refluxed, followed by a polycondensation reaction for 7 hours. After that, after cooling the temperature of the oil bath to room temperature over 3 hours, the pressure in the flask was reduced to 40 to 67 hPa to remove volatiles, the dissolved resin was cooled to room temperature, and GBL was added to adjust the solid content concentration. A solution of the novolac resin (b'-2) of cresol, which is an alkali-soluble resin adjusted to 50% by weight, was obtained. The weight average molecular weight of (b'-2) was 7000.

The structural formulas of bisphenol AF, bisphenol A, and HMOM-TPHAP used in each of the synthesis examples, comparative synthesis examples, examples, and comparative examples are shown below.

Example 1

8.0 g of an alkali-soluble resin (a-1), 2.0 g of a phenol resin (b-1), and 2.0 g of a quinone diazide compound (c-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 2

Except having used 2.0 g of phenol resin (b-2) instead of 2.0 g of phenol resin (b-1), it carried out similarly to Example 1, and obtained the varnish of a positive photosensitive resin composition. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 3

Except having used 2.0 g of phenol resin (b-3) instead of 2.0 g of phenol resin (b-1), it carried out similarly to Example 1, and obtained the varnish of a positive photosensitive resin composition. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 4

Except having used 2.0 g of phenol resin (b-4) instead of 2.0 g of phenol resin (b-1), it carried out similarly to Example 1, and obtained the varnish of a positive photosensitive resin composition. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 5

Except having used 2.0 g of phenol resin (b-5) instead of 2.0 g of phenol resin (b-1), it carried out similarly to Example 1, and obtained the varnish of a positive photosensitive resin composition. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 6

Except having used 2.0 g of phenol resin (b-6) instead of 2.0 g of phenol resin (b-1), it carried out similarly to Example 1, and obtained the varnish of a positive photosensitive resin composition. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 7

Except for using alkali-soluble resin (a-1) 9.5 g and phenol resin (b-1) 0.5 g in place of 8.0 g of alkali-soluble resin (a-1) and 2.0 g of phenol resin (b-1), In the same manner, a varnish of the positive photosensitive resin composition was obtained. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 8

In place of the alkali-soluble resin (a-1) 8.0g and the phenolic resin (b-1) 2.0g, except that the alkali-soluble resin (a-1) 9.0g and the phenolic resin (b-1) 1.0g were used, as in Example 1 In the same manner, a varnish of the positive photosensitive resin composition was obtained. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 9

In place of the alkali-soluble resin (a-1) 8.0g and the phenolic resin (b-1) 2.0g, except that the alkali-soluble resin (a-1) 5.0g and the phenolic resin (b-1) 5.0g were used, as in Example 1 In the same manner, a varnish of the positive photosensitive resin composition was obtained. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 10

In place of the alkali-soluble resin (a-1) 8.0g and the phenolic resin (b-1) 2.0g, except that the alkali-soluble resin (a-1) 3.0g and the phenolic resin (b-1) 7.0g were used, as in Example 1 In the same manner, a varnish of the positive photosensitive resin composition was obtained. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 11

A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1 except that 2.0 g of the quinone diazide compound (c-2) was used instead of 2.0 g of the quinone diazide compound (c-1). Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 12

Except having made 2.0 g of quinone diazide compound (c-1) 4.0 g, it carried out similarly to Example 1, and obtained the varnish of a positive photosensitive resin composition. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 13

Except having changed 2.0 g of quinone diazide compound (c-2) into 4.0 g, it carried out similarly to Example 11, and obtained the varnish of a positive photosensitive resin composition. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 14

In place of 8.0 g of alkali-soluble resin (a-1), except having used 8.0 g of alkali-soluble resin (a-2), in the same manner as in Example 1, a varnish of a positive photosensitive resin composition was obtained. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 15

A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1 except that 8.0 g of alkali-soluble resin (a-3) was used instead of 8.0 g of alkali-soluble resin (a-1). Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 16

A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1 except that 18.6 g of a solution of the alkali-soluble resin (a-4) (8.0 g of resin solid content) was used instead of 8.0 g of the alkali-soluble resin (a-1). Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 17

Except having added 2.0 g of thermal crosslinking agent (d-1), it carried out similarly to Example 1, and obtained the varnish of a positive photosensitive resin composition. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 18

A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1 except that 2.0 g of WPAG-336 (trade name, manufactured by Fujifilm Wako Junyaku Co., Ltd.) was used instead of 2.0 g of the quinone diazide compound (c-1). . Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 19

A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1 except that 1.0 g of a phenol compound (e-1) having a molecular weight of 100 or more and less than 500 having an electron withdrawing group and a phenolic hydroxyl group was added. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 20

A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1 except that 1.0 g of a phenol compound (e-2) having a molecular weight of 100 or more and less than 500 having an electron withdrawing group and a phenolic hydroxyl group was added. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 21

Except having used 2.0 g of phenol resin (b-8) instead of 2.0 g of phenol resin (b-1), it carried out similarly to Example 1, and obtained the varnish of a positive photosensitive resin composition. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Example 22

Except having used 2.0 g of phenol resin (b-9) instead of 2.0 g of phenol resin (b-1), it carried out similarly to Example 1, and obtained the varnish of a positive photosensitive resin composition. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Comparative Example 1

10.0 g of an alkali-soluble resin (a-1) and 2.0 g of a quinone diazide compound (c-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Comparative Example 2

The varnish of the positive photosensitive resin composition was carried out in the same manner as in Comparative Example 1 except that 8.0 g of alkali-soluble resin (a-1) and 2.0 g of phenol resin (b'-1) were used instead of 10.0 g of alkali-soluble resin (a-1). Got it. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Comparative Example 3

The varnish of the positive photosensitive resin composition was carried out in the same manner as in Comparative Example 1 except that 8.0 g of alkali-soluble resin (a-1) and 2.0 g of phenol resin (b'-2) were used instead of 10.0 g of alkali-soluble resin (a-1). Got it. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Comparative Example 4

A varnish of a positive photosensitive resin composition was obtained in the same manner as in Comparative Example 1 except that 2.0 g of the quinone diazide compound (c-2) was used instead of 2.0 g of the quinone diazide compound (c-1). Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Comparative Example 5

A varnish of a positive photosensitive resin composition was obtained in the same manner as in Comparative Example 1 except that 2.0 g of the quinone diazide compound (c-1) was 4.0 g. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Comparative Example 6

A varnish of a positive photosensitive resin composition was obtained in the same manner as in Comparative Example 4 except that 2.0 g of the quinone diazide compound (c-2) was 4.0 g. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

Comparative Example 7

A varnish of a positive photosensitive resin composition was obtained in the same manner as in Comparative Example 1 except that 2.0 g of WPAG-336 (trade name, manufactured by Fujifilm Wako Junyaku Co., Ltd.) was used instead of 2.0 g of the quinone diazide compound (c-1). . Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display were evaluated as described above.

The composition and evaluation results of each Example and Comparative Example are shown in Tables 1 to 2.

1: TFT (thin film transistor)
2: wiring
3: TFT insulating layer
4: planarization layer
5: ITO (transparent electrode)
6: substrate
7: contact hall
8: insulating layer
9: silicon wafer
10: Al pad
11: Passivation layer
12: insulating layer
13: Metal (Cr, Ti, etc.) layer
14: metal wiring (Al, Cu, etc.)
15: insulating layer
16: barrier metal
17: scribe line
18: solder bump
19: alkali-free glass substrate
20: first electrode (transparent electrode)
21: auxiliary electrode
22: insulating layer
23: organic EL layer
24: second electrode (non-transparent electrode)
25: polyimide film substrate
26: cured film

Claims (19)

A photosensitive resin composition comprising an alkali-soluble resin (a), a phenol resin (b) having a halogen atom, and a photosensitive compound (c). The method of claim 1,
The photosensitive resin composition, wherein the phenol resin (b) having a halogen atom has a structural unit represented by General Formula (1) and/or General Formula (2).

(In general formulas (1) and (2), A represents a divalent substituent having a halogen atom. R ¹ , R ² , R ⁵ , and R ⁶ each independently represent a hydrogen atom or may have 1 to 10 carbon atoms which may be substituted. Represents a hydrocarbon group, a methylol group, or an alkoxymethyl group of R ³ , R ⁴ , R ⁷ and R ⁸ each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, p is 0 to 2, q Is 0 to 4, r and s represent integers of 0 to 3.) The method according to claim 1 or 2,
The photosensitive resin composition, wherein the halogen atom of the phenol resin (b) having a halogen atom contains a fluorine atom. The method of claim 2,
A photosensitive resin composition in which A in the general formula (1) and/or the general formula (2) is -C(CF ₃ ) _{2 -.} The method according to any one of claims 1 to 4,
The photosensitive resin composition, wherein the alkali-soluble resin (a) contains polyimide, polybenzoxazole, polyamideimide, a precursor of any of them and/or a copolymer thereof. The method according to any one of claims 1 to 5,
The photosensitive resin composition, wherein the content of the phenol resin (b) having a halogen atom is 10 to 100 parts by mass based on 100 parts by mass of the alkali-soluble resin (a). The method according to any one of claims 1 to 6,
The phenol resin (b) having a halogen atom is represented by the general formula (1) and/or the general formula (2) with respect to 100 mol% of the total repeating units constituting the phenol resin (b) having the halogen atom. The photosensitive resin composition which has 50-100 mol% of a structure as a repeating unit. The method according to any one of claims 1 to 7,
The photosensitive resin composition, wherein the content of the photosensitive compound (c) is 25 to 100 parts by mass based on 100 parts by mass in total of the alkali-soluble resin (a) and the resin (b). The method according to any one of claims 1 to 8,
The photosensitive resin composition, wherein the photosensitive compound (c) contains a quinone diazide compound. The method according to any one of claims 1 to 9,
Moreover, the photosensitive resin composition containing a thermal crosslinking agent (d). The method according to any one of claims 1 to 9,
Further, a photosensitive resin composition comprising a phenol compound (e) having a molecular weight of 100 or more and less than 500 having an electron withdrawing group and a phenolic hydroxyl group. A photosensitive resin sheet formed from the photosensitive resin composition according to any one of claims 1 to 11. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 11 or the photosensitive resin sheet according to claim 12. An organic EL display device having a driving circuit, a planarization layer, a first electrode, an insulating layer, a light emitting layer, and a second electrode on a substrate, wherein the planarization layer and/or the insulating layer comprises the cured film according to claim 13. EL display device. The method of claim 14,
The organic EL display device, wherein the substrate comprises a resin film. The method of claim 14 or 15,
At least a portion of the planarization layer and/or the insulating layer has a bendable portion and/or a portion fixed in a bent state, and the curvature radius of the bendable portion and/or the portion fixed in the bent state is 0.1 mm or more 5 An organic EL display device in the range of mm or less. The method according to any one of claims 14 to 16,
The organic EL display device, wherein the planarization layer includes multiple layers. A semiconductor electronic component or semiconductor device having an electrode, a metal wiring, an interlayer insulating layer and/or a surface protective layer on a substrate, wherein the interlayer insulating layer and/or a surface protective layer comprises the cured film according to claim 13 Electronic component or semiconductor device. On a substrate, a step of forming a photosensitive resin film using the photosensitive resin composition according to any one of claims 1 to 11 or the photosensitive resin sheet according to claim 12, a step of exposing the photosensitive resin film, and the exposed photosensitivity A method of manufacturing an organic EL display device comprising a step of developing a resin film and a step of heat treating the developed photosensitive resin film.

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